EP2523742A1 - Wasserwaschverfahren und system für ein kohlenstoffdioxideinfangverfahren - Google Patents

Wasserwaschverfahren und system für ein kohlenstoffdioxideinfangverfahren

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Publication number
EP2523742A1
EP2523742A1 EP11701316A EP11701316A EP2523742A1 EP 2523742 A1 EP2523742 A1 EP 2523742A1 EP 11701316 A EP11701316 A EP 11701316A EP 11701316 A EP11701316 A EP 11701316A EP 2523742 A1 EP2523742 A1 EP 2523742A1
Authority
EP
European Patent Office
Prior art keywords
flue gas
wash water
solvent
water
solvent containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11701316A
Other languages
English (en)
French (fr)
Other versions
EP2523742B1 (de
Inventor
Barath Baburao
Michael W. Pontbriand
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Technology GmbH
Original Assignee
Alstom Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alstom Technology AG filed Critical Alstom Technology AG
Publication of EP2523742A1 publication Critical patent/EP2523742A1/de
Application granted granted Critical
Publication of EP2523742B1 publication Critical patent/EP2523742B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present disclosure relates to a water wash system for a carbon dioxide (C0 2 ) capture process. More particularly, the present disclosure relates to a method and system of washing flue gas after C0 2 absorption to reduce solvent emissions and maintain water neutrality.
  • C0 2 carbon dioxide
  • a solvent-based method for removing C0 2 with the use of amines is provided in U.S. Pat. No. 5,318,758, which is incorporated by reference herein in its entirety.
  • the '758 patent proposes a method which performs decarbonation by using an aqueous solution of an amine compound as a solution for absorbing carbon dioxide from the flue gas within an absorber column.
  • a solvent-based method for removing C0 2 from a flue gas includes a flue gas supplied by a combustion gas supply blower, which is cooled by a cooling tower, and then fed to an absorption column.
  • the fed flue gas is brought into countercurrent contact with an absorbing solution supplied through an absorbing solution supply port via at least one nozzle.
  • C0 2 in the flue gas is absorbed and removed by the absorbing solution.
  • the loaded absorbing solution which has absorbed C0 2 , is sent to a regeneration tower by the absorbing solution discharge pump through an absorbing solution discharge port.
  • the regeneration tower the loaded absorbing solution is regenerated, and fed again to the absorption tower through the absorbing solution supply port.
  • temperature bulge in the column could be in the top, bottom or middle section of the absorber column. Owing to this temperature increase, there are some solvent losses that occur in the process along the column. These solvent losses occur mainly through the decarbonated flue gas that is leaving the top of the absorber column.
  • a wash section may be included on top of the absorber column to reduce this emission loss.
  • decarbonated flue gas contacts the wash water in the wash section on top of the absorber, which captures some of the solvent from the gas phase and is recovered in the liquid phase.
  • This recovered solvent in the liquid phase can be either used directly in the C0 2 absorption process or sent to a solvent make-up section.
  • a method for recovering a solvent from a decarbonated flue gas in a water wash section of an absorption column comprising: bringing a water stream substantially free of the solvent into counter-current contact with the decarbonated flue gas in an emission control section of the absorption column to recover the solvent from the decarbonated flue gas to form a solvent containing wash water and a reduced solvent containing flue gas; and bringing a cooled wash water into counter-current contact with the reduced solvent containing flue gas in a flue gas cooling section of the absorption column to cool the reduced solvent containing flue gas, thereby forming a cooled flue gas and a used wash water.
  • a system for recovering a solvent from a decarbonated flue gas in an absorption column comprising: an emission control section configured to bring a water stream substantially free of the solvent into contact with the decarbonated flue gas to recover the solvent from the decarbonated flue gas and to form a solvent containing wash water and a reduced solvent containing flue gas; and a flue gas cooling section configured to bring cooled wash water into contact with the reduced solvent containing flue gas to cool the reduced solvent containing flue gas and condense water from the decarbonated flue gas thereby forming a cooled flue gas and used wash water.
  • FIG. 1 depicts a C0 2 -absorption column having a water wash section in accordance with an embodiment described herein;
  • FIG.2 depicts a C0 2 -absorption column having a water wash section in accordance with an embodiment described herein.
  • FIG. 1 illustrates an absorption column 100 having at least one absorber bed 110 and a water wash section 112.
  • the water wash section 1 12 is divided in to at least two sections, namely, an emission control section 114 and a flue gas cooling section 116.
  • carbon dioxide (C0 2 ) present in the flue gas 118 is absorbed by contacting the flue gas with a C0 2 - absorbing solution 119 in a countercurrent fashion.
  • the C0 2 -absorbing solution 119 is an amine-containing solution.
  • amines include, but are not limited to, for example, alkanolamine, monoethanolamine and the like, and combinations and/or mixtures thereof, which are hereinafter referred to as "amines" or "amine
  • the amine-containing solution may also include a promoter to enhance the chemical reaction kinetics involved in the capture of C02 by the ammoniated solution.
  • the promoter may include an amine (e.g. piperazine) or an enzyme (e.g., carbonic anhydrase or its analogs), which may be in the form of a solution or immobilized on a solid or semi-solid surface.
  • the decarbonated flue gas 120 contains, for example, an amount of the C0 2 -absorbing solution in vapor form, (hereinafter "a solvent").
  • a solvent an amount of the C0 2 -absorbing solution in vapor form
  • the decarbonated flue gas 120 may contain an amount of amine solvent in vapor form.
  • the decarbonated flue gas 120 ascends at least a portion of the length L of the absorption column 100 and encounters the water wash section 112. As shown in FIG. 1, the decarbonated flue gas 120 encounters the emission control section 114, which facilitates the reduction or removal of the solvent from the decarbonated flue gas.
  • the emission control section 114 includes a water stream 122 (also referred to as "make-up water”).
  • the water stream 122 is relatively free of contaminants and impurities, such as, for example, the solvent, and facilitates the absorption of the solvent from the decarbonated flue gas 120. While not shown on the figure, it is contemplated that the water stream 122 can be used from anywhere within the process itself, e.g., regenerator condensate, and the like.
  • the decarbonated flue gas 120 comes into contact with water stream 122 in a countercurrent fashion as the decarbonated flue gas ascends up at least a portion of the length L of the absorption column 100 and the water stream descends at least a portion of the absorption column.
  • the concentration gradient of solvent e.g., amine
  • solvent e.g., amine
  • the reduced solvent containing flue gas 124 leaving the emission control section 114 is almost free of any solvent, therefore vapor phase solvent losses are reduced.
  • the water circulation rate for the emission control section 1 14 is very low. This in turn affects the temperature of the flue gas 124 exiting the emission control section 114.
  • the flue gas 124 is provided to the flue gas cooling section 116 by ascending at least a portion of the length L of the absorption column 100. [0023] In the flue gas cooling section 116, the solvent emissions control is very minimal, and therefore, the used wash water 126 from the flue gas cooling section 116 may be used elsewhere in the absorption column 100 or within the overall process of removing
  • the flue gas cooling section 1 16 includes a liquid distributor 128.
  • the liquid distributor 128 may include, for example, a manifold 130 having nozzles or the like to disperse a wash water 132 within the absorption column 100, and a liquid distribution plate 134 or the like, to further distribute the wash water within the absorption column.
  • the flue gas cooling section 116 may also include a mass transfer device 136, such as packing trays, plates, or the like, disposed beneath the liquid distributor 128. As shown in FIG. 1, the mass transfer device 136 is positioned beneath the liquid distribution plate 134.
  • the flue gas cooling section 116 may also include a collection device 138, such as a liquid collector plate, disposed beneath the mass transfer device 136, which acts to collect wash water 132 that has descended at least a portion of the length L of the absorption column 100.
  • the collection device 138 provides the wash water to a sump 140, where the wash water is withdrawn as used wash water 126.
  • a pump 142 is in fluid communication (e.g., by piping, tubing, ductwork, or the like) with the sump 140 of the collection device 128.
  • the pump 142 facilitates removal of the water collected by the collection device 138 and provided to the sump 140.
  • a heat exchanger 144 is in fluid communication with the pump 142 and is configured to reduce the temperature of the used wash water 126 to form a cooled liquid 145. As shown in FIG. 1, at least a portion of the cooled liquid 145 is recirculated within the flue gas cooling section 116. In one embodiment, as shown in FIG. 1, the cooled liquid supplements wash water 132 that is provided to the flue gas cooling section 1 16. The system is not limited in this regarding since it is contemplated that the wash water 132 may consist entirely of the cooled liquid 145.
  • a branch line 146 is disposed in fluid communication with the pump 142 and the collection device 138.
  • the branch line 146 is arranged so less than all of the used wash water 126 may be cooled and returned to the flue gas cooling section 116.
  • a portion of the used wash water 126 may be provided to the heat exchanger 144, and a portion of the withdrawn liquid may be provided to the branch line 146.
  • 50% of the used wash water 126 is provided to the heat exchanger 144 and 50 % of the used wash water is provided to the branch line 146.
  • the branch line 146 may include one or more control valves 148 or other flow control devices, to adjust an amount of used wash water 126 removed from the water wash system 112 or to adjust an amount of used wash water that flows through the branch line.
  • the used wash water 126 provided to branch line 146 may be sent to a lean solvent make-up tank (not shown) or to the top of the absorption column 100 (not shown).
  • the used wash water 126 because it contains little to no amine solvent, may also be used elsewhere within the overall flue gas treatment system.
  • the emission control section 114 also includes a collection device 150 for collecting wash water in the emission control section.
  • the collection device 150 is disposed between a material transfer device 152 and an absorbing solution distributor 154.
  • the absorbing solution distributor 154 facilitates the distribution of the C0 2 -absorbing solution 119 throughout the absorber bed 110.
  • the C0 2 - absorbing solution 119 contacts the flue gas 118 in a countercurrent manner as the flue gas 118 ascends at least to a portion of a length L of the absorption column 100 and the C0 2 - absorbing solution travels in an opposite direction.
  • a liquid distributor 156 (also referred to as a fluid distribution device) is disposed within the absorption column 100 and is in fluid communication with the source of the water stream 122.
  • the liquid distributor 156 is configured to distribute the water stream 122 within the emission control section 114.
  • a branch line 158 is disposed in fluid communication with a sump 160 of the collection device 150.
  • the branch line 158 may be in fluid communication with branch line 146, and may include one or more control valves 162 or of the flow control devices, to adjust an amount of solvent containing 161 wash water that is withdrawn from the emissions control section 114.
  • Solvent containing wash water 161 from the emission control system 114 may be sent to a lean solvent make-up tank (not shown) or to the top of the absorption columns 100, or used within the overall system for removing contaminants from the flue gas.
  • a controller 164 may be in communication with one or more components described above.
  • the controller 164 may be, for example, a general purpose computer, an application-specific integrated circuit, or a pneumatic, electric or mechanical controller.
  • the controller 164 may be configured to automatically adjust one or more system parameters to control solvent emissions and maintain water neutrality in the wash water system 1 12 or the entire C0 2 removal system.
  • the controller 164 may be in communication with the heat exchanger 144, the pump 142 or the flow control valves 148, 162.
  • the system is not limited in this regard as the controller 164 may be in communication with other components.
  • the controller 164 can be configured to adjust an amount of solvent, e.g., amine, that is recovered by the wash water system 1 12 by adjusting an amount of the water stream 122 that is brought into contact with decarbonated flue gas 120. For example, if the controller 164 determines that solvent emission or system solvent losses meet or exceed a predetermined threshold, the controller 164 may act to increase the amount of water stream 122 added to the emission control section 1 14.
  • solvent e.g., amine
  • the controller 164 can also be configured to control water neutrality by adjusting a temperature of the wash water 132 brought into contact with the decarbonated flue gas 120 in the flue gas cooling section 1 16, thereby adjusting the amount of water removed from the reduced solvent containing flue gas 124.
  • Water neutrality can also be controlled, for example, by assessing or determining the amount of water stream 122 added to the water wash section 112 (for water wash neutrality) or the entire C0 2 system (for system neutrality) and compared to the amount of water removed from the flue gas cooling section 1 16 (e.g., by pump 142 or branch line 146).
  • the controller may increase or decrease the temperature of the wash water 132 (e.g., by adjusting the flow of the wash water to the heat exchanger 144) to adjust an amount of water removed from the reduced solvent containing flue gas 124, and thereby maintain water neutrality within a desired range.
  • the controller 164 may be capable of measuring or determining a solvent concentration, collected in the absorption column 100, for example, and adjust the temperature of the wash water if the solvent concentration meets certain thresholds.
  • the controller 164 may also control the amount of the used wash water 126 provided to branch line 146 by adjusting one or more of the flow control valve 148 or the pump 142.
  • the liquid distributor 156 of the emission control section 1 14 may comprise, for example, a manifold 166 with nozzles or the like to disperse the water stream 122 within the column, and a liquid distribution plate 168 or the like to further distribute the wash water within the column 100.
  • the absorption column 100 which includes the wash section 112 and related components as described in detail above, is configured to recirculate at least a portion of the used wash water to the flue gas cooling section 116 and provide at least a portion of the withdrawn liquid to the emission control section 114.
  • the sump 140 is in fluid communication with the pump 142,
  • the pump 142 withdraws the used wash water 126 from the sump 140. After being withdrawn, at least a portion of the used wash water 126 is provided to the heat exchanger 144 as described in more detail above. Another portion of the used wash water 126 is provided to the emission control section 114.
  • the amount of used wash water 126 is provided to the emission control section 114 may be controlled by opening or closing a control valve 170 that is positioned between the flue gas cooling section 1 16 and the emission control section 1 14.
  • Control valve 170 may be operated manually or automatically.
  • Control valve 170 may be in communication with the controller 164, which may close or open control valve 170 based on information, readings, or signals concerning amounts of wash water provided to the emission control section 1 14 by other sources as described herein.
  • the used wash water 126 may be recirculated for re-use in the flue gas cooling section 1 16 or provided to the emission control section 1 14. Re-use of the used wash water 126 may reduce the amount of fresh water provided to the absorption tower in the form of water stream 122 and wash water 132.
  • Increasing an amount of water provided to the emission control section 114 facilitates proper circulation and distribution of water that comes into countercurrent contact with the decarbonated flue gas 120.
  • the desired amount of solvent can be removed from the decarbonated flue gas 120.
  • Maintenance or proper circulation of water in the emission control sectionl 14 can be achieved by providing the used wash water 126 to the emission control section.
  • At least a portion of the solvent containing wash water 161 withdrawn from sump 160 by a pump 172 into a branch line 158 may be recirculated and provided to the top of the emission control section.
  • At least a portion of the solvent containing wash water 161 in branch line 158 is directed by line 174 to join with at least a portion of used wash water 126 to form a recycle liquid 176.
  • Recycle liquid 176 is introduced to the top of the emission control section 114 via the manifold 166. Once introduced to the emission control section 114, the recycle liquid 176, along with water stream 122, descends at least a length L of the absorption tower 100, thereby absorbing the solvent from the decarbonated flue gas 120 to form flue gas 124.
  • the amount of the solvent containing wash water 161 provided to the emission control section 114 may be regulated by a control valve 178.
  • the control valve 178 is disposed in line 174, however, it is contemplated that the control valve 178 may be disposed in the branch line 158.
  • the control valve 178 may be in communication with the controller 164, which may close or open the control valve 178 based on information, readings or signals concerning amounts of the wash water provided to the emission control section 114 by other sources described herein.
  • Table 1 Com arison of conventional and new water wash scheme
  • FIG. 2 To illustrate the effectiveness of the system shown in FIG. 2, a simulation was run to show the impact on the solvent emissions as well as water neutrality. The system of FIG. 2 was compared to a conventional system, i.e., having only one wash water bed as well as a system according to FIG. 1.
  • Table 2 Com arison of Conventional S stems to S stems Illustrated in FIGS. 1 and 2

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
EP11701316.9A 2010-01-14 2011-01-10 Wasserwaschverfahren für ein kohlenstoffdioxideinfangverfahren Active EP2523742B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US29497110P 2010-01-14 2010-01-14
US12/985,613 US9314734B2 (en) 2010-01-14 2011-01-06 Wash water method and system for a carbon dioxide capture process
PCT/US2011/020631 WO2011087972A1 (en) 2010-01-14 2011-01-10 Water wash method and system for a carbon dioxide capture process

Publications (2)

Publication Number Publication Date
EP2523742A1 true EP2523742A1 (de) 2012-11-21
EP2523742B1 EP2523742B1 (de) 2017-04-12

Family

ID=44257490

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11701316.9A Active EP2523742B1 (de) 2010-01-14 2011-01-10 Wasserwaschverfahren für ein kohlenstoffdioxideinfangverfahren

Country Status (17)

Country Link
US (1) US9314734B2 (de)
EP (1) EP2523742B1 (de)
JP (1) JP5881617B2 (de)
KR (1) KR101441512B1 (de)
CN (2) CN102781551A (de)
AU (1) AU2011205517B2 (de)
BR (1) BR112012017438B1 (de)
CA (1) CA2786997C (de)
ES (1) ES2627584T3 (de)
IL (1) IL220897A (de)
MA (1) MA33943B1 (de)
MX (1) MX338470B (de)
PL (1) PL2523742T3 (de)
RU (1) RU2558361C2 (de)
SG (3) SG182503A1 (de)
WO (1) WO2011087972A1 (de)
ZA (1) ZA201205533B (de)

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CN107008105B (zh) 2018-11-02
EP2523742B1 (de) 2017-04-12
CA2786997C (en) 2015-03-17
ES2627584T3 (es) 2017-07-28
CN102781551A (zh) 2012-11-14
BR112012017438B1 (pt) 2020-02-04
WO2011087972A1 (en) 2011-07-21
SG10201502866PA (en) 2015-06-29
US9314734B2 (en) 2016-04-19
MX338470B (es) 2016-04-18
MX2012008121A (es) 2012-09-12
ZA201205533B (en) 2013-09-25
MA33943B1 (fr) 2013-01-02
KR20120098929A (ko) 2012-09-05
IL220897A (en) 2016-11-30
AU2011205517A1 (en) 2012-08-09
US20110168020A1 (en) 2011-07-14
CN107008105A (zh) 2017-08-04
SG182503A1 (en) 2012-08-30
AU2011205517B2 (en) 2016-05-19
CA2786997A1 (en) 2011-07-21
RU2012131551A (ru) 2014-01-27
IL220897A0 (en) 2012-09-24
SG10201502865RA (en) 2015-05-28
KR101441512B1 (ko) 2014-11-03
JP2013517126A (ja) 2013-05-16
PL2523742T3 (pl) 2017-09-29
BR112012017438A2 (pt) 2016-04-19
JP5881617B2 (ja) 2016-03-09
RU2558361C2 (ru) 2015-08-10

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